Cadmium accumulation and Cd-binding proteins in marine invertebrates--a radiotracer study

Tissue and subcellular accumulation of cadmium were studied in different tissues of three marine invertebrates (blue mussel Mytilus edulis, the tunicate Ciona intestinalis and the sea star Asterias rubens) using radioactive ¹⁰⁹Cd as a tracer. The organisms were exposed to 0.05, 2 and 50 μg Cd l⁻¹ for 21 days. Quantitative data were obtained by dissecting, weighing and subsequently measuring radioactivity in organs and tissues. Differences between each exposure and each tissue with regard to the amount of radioactivity and metallothionein (MT) content were evaluated. Obvious interspecies differences in Cd accumulation were observed, as well as differences between tissues of the three species. The highest concentrations of Cd in all exposure treatments were found in the hepatopancreas of M. edulis and body wall of A. rubens. Taking all treatments into account, Cd accumulation in the tunic of C. intestinalis was high compared to other tissues from this species. Over 60% of Cd was present in the S50 fraction in all treatments in all three species. Metallothionein levels were increased at the highest Cd-exposure in all species and tissues, except in branchial pharynx of C. intestinalis where the highest MT level was reached following exposure to 2 μg Cd l⁻¹. The most surprising finding was that even the lowest Cd exposure concentration (0.05 μg Cd l⁻¹) caused MT induction in pyloric caeca of A. rubens, but there was no dose-dependent increase in MT at higher exposure levels.     

Effects of cadmium and zinc on oxygen consumption, ammonium excretion, and osmoregulation of white shrimp (Litopenaeus vannamei)

White shrimp, Litopenaeus vannamei, a globally important cultured prawn species, is an ideal animal for studying the impairment caused by the effects of heavy metals that are often detected in coastal areas. The main purpose of the present study was to detect the acute toxicity of Cd and Zn to L. vannamei, and to investigate their effects on gill functions, which have not been carried out in this species before, hoping to obtain some important significance. First of all, we examined the acute toxicity of cadmium (Cd) and zinc (Zn) to L. vannamei and obtained 24-, 48-, 72-, and 96-h medium lethal concentration (LC₅₀) values of 2.58, 1.30, 1.14, and 1.07 mg Cd l⁻¹ and 3.98, 2.14, 1.75, and 1.35 mg Zn l⁻¹, respectively. Furthermore, we also found that exposure of shrimp to Cd or Zn caused an inhibition in oxygen consumption of 91.3% and 75.9% lower than that of the control. However, after separate exposure to Cd or Zn, elevations in ammonium excretion were obtained, which were 153.7% and 144.1%, respectively, higher than the control. It is most likely that elevations in ammonium excretion were related to decreased osmotic pressure of shrimp blood. Finally, the distribution of Cd and Zn within gills was also determined.     

Assessment of toxicity of a glyphosate-based formulation using bacterial systems in lake water

A new Aeromonas bioassay is described to assess the potential harmful effects of the glyphosate-based herbicide, Roundup^®, in the Albufera lake, a protected area near Valencia. Viability markers as membrane integrity, culturability and β-galactosidase production of Aeromonas caviae were studied to determine the influence of the herbicide in the bacterial cells. Data from the multifactor analysis of variance test showed no significant differences (P > 0.05) between A. caviae counts of viability markers at the studied concentrations (0, 50 and 100 mg l⁻¹ of glyphosate).

The effects of Roundup^® on microbial biota present in the lake were assessed by measuring the number of indigenous mesophilic Aeromonas in presence of different amounts of the herbicide at 0, 50 and 100 mg l⁻¹ of glyphosate. In samples containing 50 and 100 mg l⁻¹ of glyphosate a significant (P < 0.05) increase in Aeromonas spp. counts and accompanying flora was observed.

The acute toxicity of Roundup^® and of Roundup^® diluted with Albufera lake water to Microtox^® luminescent bacterium (Vibrio fischeri) also was determined. The EC₅₀ values obtained were 36.4 mg l⁻¹ and 64.0 mg l⁻¹ of glyphosate respectively. The acidity (pH 4.5) of the herbicide formulation was the responsible of the observed toxicity.     

Biotransformation and antioxidant response in Ceratophyllum demersum experimentally exposed to 1,2- and 1,4-dichlorobenzene

We report the effects of 1,2- and 1,4-dichlorobenzene (1,2-DCB and 1,4-DCB) on the aquatic macrophyte Ceratophyllum demersum. We evaluated the response of the antioxidant system through the assay of glutathione reductase (GR), guaiacol peroxidase (POD) and glutathione peroxidase (GPx). Additionally, the effect of DCBs on the detoxication system by measuring the activity of glutathione-S-transferase (GST) was evaluated.

C. demersum showed elevated GST activities when exposed to 10 and 20 mg l⁻¹ 1,2-DCB, and at 10 mg l⁻¹ for 1,4-DCB. These results show that glutathione conjugation take place at relatively high concentrations of both isomers. Significantly increased activities of POD were also detected in C. demersum exposed to concentrations above 5 mg l⁻¹ of the corresponding isomer.

The GR activity was enhanced in plants exposed to 1,2-DCB (5 mg l⁻¹) and 1,4-DCB (10 mg l⁻¹). GPx was also significantly increased in exposures to the corresponding isomer, each at a concentration of 10 mg l⁻¹. However, plants exposed to low doses of 1,4-DCB (1 mg l⁻¹) showed significantly decreased activities of both enzymes GR and GPx.

Consequently, it is clear that the exposure of the aquatic macrophyte C. demersum to DCBs is able to cause an activation of the antioxidant system, showing an isomer specific pattern, which suggests that the defence system of this plant is playing an important role in scavenging ROS, helping to protect the organism against adverse oxidative effects generated by the prooxidant action of the tested xenobiotics. Furthermore, increased GST activities give indirect evidence on the conjugation of either DCBs or the corresponding metabolites during phase II of detoxication, which supports the elimination process of toxic metabolites from cells of C. demersum.     

Feasibility of phosphate fertilizer to immobilize cadmium in a field

To reduce effectively cadmium (Cd) phytoextractability by phosphate fertilizer in Cd contaminated soil, fused and superphosphate (FSP) was applied at the rate of 0, 33.5 (recommendation level), 167.5, and 335 kg P ha⁻¹ for radish (Raphanus sativa L.). Unlike from what we expected, soil Cd extractability and Cd concentration in radish increased with increasing FSP application in the field. To determine the effect of FSP on Cd immobilization, FSP was mixed with the selected soil at the rate of 0, 200, 400, 800, and 1600 mg P kg⁻¹ and then incubated for 8 weeks. As observed in the field study, NH₄OAc extractable Cd concentration increased slightly with FSP addition up to 400 mg P kg⁻¹ and thereafter dramatically decreased upon increasing its application rate. Soil pH and negative charge were decreased at low level of FSP application up to 400 mg P kg⁻¹, but thereafter continually increased with increasing application level. This could be indirect evidence that net soil negative charge was increased by the specific adsorption of phosphate at the high rate of FSP application over 400 mg P kg⁻¹. The labile Cd fraction (water soluble and exchangeable + acidic fraction) increased with increasing FSP application by 400 mg P kg⁻¹ and thereafter gradually decreased with corresponding increase in unlabile fraction (oxidizable and residual fraction). Based on these results, FSP might be applied with a very high rate over 800 mg P kg⁻¹ to decrease Cd extractability in the selected field. However, this level is equivalent to 1440 kg P ha⁻¹, which is about 43 times higher than the recommendation levels for radish production and resulted in a significant increase in water soluble P concentration creating a new environmental problem. Therefore, the feasibility of FSP to reduce Cd extractability in the field is very low.     

Accumulation, speciation and cellular localization of copper in Sesbania drummondii

Growth, accumulation and intracellular speciation and distribution of copper (Cu) in Sesbania drummondii was studied using scanning-electron microscopy (SEM), X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). The growth of seedlings was assessed in terms of biomass accumulation. The growth of the seedling was enhanced by 73.5% at a low Cu concentration (50 mg l⁻¹) compared to the control treatment. Additionally, seedling growth was inhibited by 18% at 300 mg l⁻¹ Cu with respect to the control. Copper concentration in roots and shoots was increased with increasing Cu concentration in the growth solution. The accumulation of Cu was found to be higher in roots than in the shoots. At a concentration of 300 mg l⁻¹ Cu, the roots accumulated 27,440 mg Cu kg⁻¹ dry weight (dw) while shoots accumulated 1282 mg Cu kg⁻¹ dw. Seedlings were assessed for photosynthetic activity by measuring chlorophyll a fluorescence parameters: F_v/F_m and F_v/F₀ values. Photosynthetic integrity was not affected by any of the Cu treatments. The X-ray absorption spectroscopic (XAS) studies showed that Cu was predominantly present as Cu(II) in Sesbania tissue. In addition, from the XAS studies it was shown that the Cu exists in a mixture of different coordination states consisting of Cu bound to sugars and small organic acids with some possible precipitated copper oxide. From the EXAFS studies, the coordination of Cu was determined to have four equatorial oxygen(nitrogen) ligands at 1.96 Å and two axial oxygen ligands at 2.31 Å. Scanning-electron microscopy studies revealed the distribution of Cu within the seedlings tissues, predominantly accumulated in the cortical and vascular (xylem) regions of root tissues. In the stem, most of the Cu was found within the xylem tissue. However, the deposition of Cu within the leaf tissues was in the parenchyma. The present study demonstrates the mechanisms employed by S. drummondii for Cu uptake and its biotransformation.     

Direct measurement of denitrification activity in a Gulf coast freshwater marsh receiving diverted Mississippi River water

Wetland loss along the Louisiana Gulf coast and excessive nitrate loading into the Gulf of Mexico are interrelated environmental problems. Nitrate removal by soil denitrification activity was studied in a ponded freshwater marsh receiving diverted Mississippi River water for the purpose of reversing or slowing wetland loss. Labeled ¹⁵N-nitrate was applied at 3.8 g N m⁻² into four replicate study plots after removing above ground vegetation. Nitrogen gas (N₂) and nitrous oxide (N₂O) emissions from the plots were determined by isotope ratio mass spectrometry (IRMS). Nitrous oxide emissions were also compared with the results determined by gas chromatograph (GC). Results showed that it took 2 weeks to remove the added nitrate with N₂O emission occurring over a period of 4 d. The apparent denitrification dynamics were assumed to follow the Michaelis–Menten equation. The maximum denitrification rate and K_m value were determined as 12.6 mg N m ⁻² h⁻¹, and 6.5 mg N l⁻¹, respectively. Therefore the maximum capacity for nitrate removal by the marsh soil would be equivalent to 110 g N m⁻² yr⁻¹, with more than 30% of nitrogen gas evolved as N₂O. For typical nitrate concentrations in Mississippi River water of about 1 mg N l⁻¹, nitrate would be removed at a rate of 14.7 g N m⁻² yr⁻¹ with N₂O emission about 1.5%. A denitrification dynamic model showed that the efficiency of nitrate removal would largely depend on the water discharge rate into the ponded wetland. Higher discharge rate will result in less retention time for the water in the marsh where nitrate is denitrified.     

UV-H2O2 based AOP and its integration with biological activated carbon treatment for DBP reduction in drinking water

The presence of disinfection byproducts (DBPs) such as trihalomethanes (THMs) and haloacetic acids (HAAs) in drinking water is of great concern due to their adverse effects on human health. Emerging regulation limiting the concentration of DBPs in drinking water has increased demands for technologies and processes which reduce the formation of DBPs in drinking water. In this study, UV-H₂O₂ based advance oxidation process (AOP) was used to treat raw surface water. Experiments were conducted using low pressure mercury vapor UV lamps in collimated beam and flow-through annular photoreactors. The effect of UV fluence (0–3500 mJ cm⁻²) and hydrogen peroxide concentration (0–23 mg l⁻¹) in reducing the concentration of THMs and HAAs was examined. The UV-H₂O₂ AOP was then coupled with a downstream biological activated carbon (BAC) treatment to assess the synergetic benefits of combining the two treatments. It was observed that UV-H₂O₂ AOP was only effective at reducing DBPs at UV fluences of more than 1000 mJ cm⁻²and initial H₂O₂ concentrations of about or greater than 23 mg l⁻¹. However, the combined AOP–BAC treatment showed significant reductions of 43%, 52%, and 59% relative to untreated raw water for DBPs, TOC, and UV₂₅₄, respectively.     

Toxicity of HC Orange No. 1 to Daphnia magna, zebrafish (Brachydanio rerio) embryos, and goldfish (Carassius auratus)

HC Orange No. 1 (HCO1; 2-nitro-4′-hydroxydiphenylamine) (CAS No. 54381-08-7) is used as a color additive in hair dyes and can be released into aquatic environments in wastewater. In this paper, the effects of HCO1 on aquatic organisms were studied using a battery of toxicological tests. These included measuring immobilization of Daphnia magna, inhibition of zebrafish embryo development, and acute lethality in zebrafish and goldfish, which are different species belonging to different trophic levels. HCO1 was toxic to all of the organisms studied. In our experiments, HCO1 remarkably restrained the mobility of D. magna, which may cause subsequent death. The EC₅₀ value for restrained the mobility of D. magna at 48 h was 1.54 mg HCO1 l⁻¹. In addition, HCO1 showed toxicity in zebrafish and goldfish, where LC₅₀values at 96 h were 4.04 and 5.37 mg l⁻¹, respectively. The results also indicated that HCO1 remarkably retarded the development of zebrafish embryos, which may cause embryo abnormality and even lethality. The most sensitive toxicological endpoint in the development of the embryos was failure to hatch, which had an EC₅₀ of 0.19 mg HCO1 l⁻¹. These results indicated that HCO1 is a potential teratogen to zebrafish embryos. In addition, as HCO1 concentrations increased, the outcomes of each of these toxicity tests changed in a concentration-dependent manner. Together, the results revealed that HCO1 appears to be toxic to multiple different species of aquatic organisms. The EC₅₀ (LC₅₀) values contain sufficient discriminatory power for risk assessment of HCO1 in aquatic environments. Based on the present results, more efficient risk assessment procedures for HCO1 will be designed in the future, integrating more flexible testing methods into the testing schemes that employ only the necessary tools for each case.     

Screening 31 endocrine-disrupting pesticides in water and surface sediment samples from Beijing Guanting reservoir

For screening 31 potential or suspected endocrine-disrupting pesticides in water and surface sediments, a multiresidue analysis method based on gas chromatography with electron capture detection (GC/ECD) was developed. Solid phase extraction (SPE) technology with Oasis^® HLB cartridge was also applied in sample extraction. The relevant mean recoveries were 70–103% and 71–103% for water and sediment, respectively. Relative standard deviations (RSD) are 2.0–7.0%, 4.0–8.0% for water and sediment, respectively. Thirty one pesticides (-HCH, β-HCH, γ-HCH, δ-HCH, hexachlorobenzene (HCB), aldrin, heptachlor, endosulfan I & II, p,p′-DDD, o,p′-DDT, p,p′-DDT, p,p′-DDE, endrin aldehyde, endosulfan sulphate, methoxychlor, hepachlor epoxide, -chlordane, γ-chlordane, dieldrin, endrin, dicofol, acetochlor, alachlor, metolachlor, chlorpyriphos, nitrofen, trifluralin, cypermethrin, fenvalerate, deltamethrin) in water and surface sediment samples from Beijing Guanting reservoir were analyzed. Concentrations of pesticides ranged from 7.59 to 36.0 ng g⁻¹ on a dry wt. basis for sediment samples, from 279.3 to 2740 ng l⁻¹ for pore waters and from 48.8 to 890 ng l⁻¹ for water samples, respectively, with a mean concentration of 10.7 ng g⁻¹ in sediment, 735 ng l⁻¹ in pore water and 295 ng l⁻¹ in water, respectively. The data obtained provides information on the levels and sources of endocrine-disrupting pesticides in Guanting reservoir. These results underscore the need to improved environmental protection measures in order to reduce the exposure of the population and aquatic biota to these endocrine-disrupting compounds.     

Arsenic removal from water employing heterogeneous photocatalysis with TiO2 immobilized in PET bottles

Arsenic oxidation (As(III) to As(V)) and As(V) removal from water were assessed by using TiO₂ immobilized in PET (polyethylene terephthalate) bottles in the presence of natural sunlight and iron salts. The effect of many parameters was sequentially studied: TiO₂ concentration of the coating solution, Fe(II) concentration, pH, solar irradiation time; dissolved organic carbon concentration. The final conditions (TiO₂ concentration of the coating solution: 10%; Fe(II): 7.0 mg l⁻¹; solar exposure time: 120 min) were applied to natural water samples spiked with 500 μg l⁻¹ As(III) in order to verify the influence of natural water matrix. After treatment, As(III) and total As concentrations were lower than the limit of quantitation (2 μg l⁻¹) of the voltammetric method used, showing a removal over 99%, and giving evidence that As(III) was effectively oxidized to As(V). The results obtained demonstrated that TiO₂ can be easily immobilized on a PET surface in order to perform As(III) oxidation in water and that this TiO₂ immobilization, combined with coprecipitation of arsenic on Fe(III) hydroxides(oxides) could be an efficient way for inorganic arsenic removal from groundwaters.     

Combined biological and photocatalytic treatment for the mineralization of phenol in water

Phenol is degraded by biological treatment, however mineralization requires long time. To decrease the time and operational cost necessary for the mineralization of phenol, an optimum operation condition of the combined biological–photocatalytical treatment was investigated. The mineralization of phenol (50 mg l⁻¹) was conducted in a flow-type biomembrane tank combined with a batch-type TiO₂-suspended photocatalytic reactor. Phenol was degraded biologically to the concentration of 6.8 mg l⁻¹, an effective concentration for further photocatalytic treatment. After the biological treatment, the biotreated phenol was treated photocatalytically to complete the mineralization of phenol. The combined treatment shortened the mineralization time compared to the biological treatment and electric cost compared to the photocatalytic treatment only. The combined treatment may be suitable for a short-time mineralization of phenol in wastewater.     

The use of physiological characteristics for comparison of organic compounds phytotoxicity

The influence of intact (FLT) and photomodified (phFLT) fluoranthene (0.05, 0.5 and 5 μmol l⁻¹) and herbicide Basagran (5, 20, 35 and 50 nmol l⁻¹) on the germination, growth of seedlings and photosynthetic processes in pea plants (Pisum sativum L., cv. Garde) was investigated. The germination was significantly inhibited already by the lowest concentration (0.05 μmol l⁻¹) of FLT and phFLT, while Basagran caused inhibition only in higher concentrations (35 and 50 nmol l⁻¹). The growth of roots was significantly inhibited by higher concentration 5 μmol l⁻¹ of both FLT and phFLT and the shoot of seedlings was significantly influenced only by photomodified form. The length of root and shoot was inhibited already by concentration 5 nmol l⁻¹ of Basagran. Organic compounds applied on chloroplasts suspension influenced primary photochemical processes of photosynthesis. In chlorophyll fluorescence parameters, the significant increase of F₀ values and the decrease of F_V/F_M and Φ_II values by application of FLT (0.5 and 5 μmol l⁻¹) and phFLT (0.05, 0.5 and 5 μmol l⁻¹) was recorded. The maximum capacity of PSII (F_V/F_M) was influenced by the highest (50 nmol l⁻¹) and the effective quantum yield of PSII (Φ_II) already by the lowest (5 nmol l⁻¹) concentration of Basagran. Hill reaction activity decreased and was significantly inhibited by higher concentration (0.5 and 5 μmol l⁻¹) of FLT and phFLT and already by the lowest concentration (5 nmol l⁻¹) of Basagran.     

Selective adsorption of phenanthrene dissolved in surfactant solution using activated carbon

Selective adsorption of a hazardous hydrophobic organic compound (HOC) by activated carbon as a means of recovering surfactants after a soil washing process was investigated. As a model system, phenanthrene was selected as a representative HOC and Triton X-100 as a nonionic surfactant. Three activated carbons that differed in size (Darco 20–40 (D20), 12–20 (D12) and 4–12 (D4) mesh sizes) were used in adsorption experiments. Adsorption of surfactant onto activated carbon showed a constant maximum above the critical micelle concentration, which were 0.30, 0.23, 0.15 g g⁻¹ for D20, D12, and D4, respectively. Selectivity for phenanthrene to Triton X-100 was much higher than 1 over a wide range of activated carbon doses (0–6 g l⁻¹) and initial phenanthrene concentrations (10–110 mg l⁻¹). Selectivity generally increased with decreasing particle size, increasing activated carbon dose, and decreasing initial concentration of phenanthrene. The highest selectivity was 74.9, 57.3, and 38.3 for D20, D12, and D4, respectively, at the initial conditions of 10 mg l⁻¹ phenanthrene, 5 g l⁻¹ Triton X-100 and 1 g l⁻¹ activated carbon. In the case of D20 at the same conditions, 86.5% of the initial phenanthrene was removed by sorption and 93.6% of the initial Triton X-100 remained in the solution following the selective adsorption process. The results suggest that the selective adsorption by activated carbon is a good alternative for surfactant recovery in a soil washing process.     

Accelerated seeded precipitation pre-treatment of municipal wastewater to reduce scaling

Membrane based treatment processes are very effective in removing salt from wastewater, but are hindered by calcium scale deposit formation. This study investigates the feasibility of removing calcium from treated sewage wastewater using accelerated seeded precipitation. The rate of calcium removal was measured during bench scale batch mode seeded precipitation experiments at pH 9.5 using various quantities of calcium carbonate as seed material. The results indicate that accelerated seeded precipitation may be a feasible option for the decrease of calcium in reverse osmosis concentrate streams during the desalination of treated sewage wastewater for irrigation purposes, promising decreased incidence of scaling and the option to control the sodium adsorption ratio and nutritional properties of the desalted water. It was found that accelerated seeded precipitation of calcium from treated sewage wastewater was largely ineffective if carried out without pre-treatment of the wastewater. Evidence was presented that suggests that phosphate may be a major interfering substance for the seeded precipitation of calcium from this type of wastewater. A pH adjustment to 9.5 followed by a 1-h equilibration period was found to be an effective pre-treatment for the removal of interferences. Calcium carbonate seed addition at 10 g l⁻¹ to wastewater that had been pre-treated in this way was found to result in calcium precipitation from supersaturated level at 60 mg l⁻¹ to saturated level at 5 mg l⁻¹. Approximately 90% reduction of the calcium level occurred 5 min after seed addition. A further 10% reduction was achieved 30 min after seed addition.     

Antimony content of macrofungi from clean and polluted areas

Species of macrofungi (mushrooms) were collected from clean areas and analyzed for their antimony content. These were compared to species collected from extremely polluted areas in the vicinity of a lead smelter and on mine and slag dumps. Antimony content was determined using long-term instrumental neutron activation analysis (INAA). Ectomycorrhizal and terrestrial saprobic macrofungi were examined. Antimony content of macrofungi from the clean areas was mostly less than 100 μg kg⁻¹ (dry mass). The highest concentrations (units of mg kg⁻¹) were found in various species of the ectomycorrhizal genera Chalciporus and Suillus. Antimony contents of macrofungi growing in the polluted areas were considerably higher. The highest content was found in a single collection of Chalciporus piperatus (1423 mg kg⁻¹).     

On the performance of Fe and Fe,F doped Ti-Pt/PbO2 electrodes in the electrooxidation of the Blue Reactive 19 dye in simulated textile wastewater

The electrochemical performance of pure Ti–Pt/β-PbO₂ electrodes, or doped with Fe and F (together or separately), in the oxidation of simulated wastewaters containing the Blue Reactive 19 dye (BR-19), using a filter-press reactor, was investigated and then compared with that of a boron-doped diamond electrode supported on a niobium substrate (Nb/BDD). The electrooxidation of the dye simulated wastewater (volume of 0.1 l, with a BR-19 initial concentration of 25 mg l⁻¹) was carried out under the following conditions: current density of 50 mA cm⁻², volume flow rate of 2.4 l h⁻¹, temperature of 25 °C and electrode area of 5 cm². The performances of the electrodes in the dye decolorization were quite similar, achieving 100% decolorization, and in some cases 90% decolorization was achieved by applying only ca. 0.3 A h l⁻¹ (8 min of electrolysis). The reduction of the simulated wastewater organic load, monitored by its total organic carbon content (TOC), was greater for the Ti–Pt/β-PbO₂–Fe,F electrode obtained from an electrodeposition bath containing 1 mM Fe³⁺ and 30 mM F⁻. In this case, after 2 h of electrolysis the obtained TOC reduction was 95%, while for the pure β-PbO₂ and the Nb/BDD electrodes the reductions were 84% and 82%, respectively.     

Octyl and nonylphenol ethoxylates and carboxylates in wastewater and sediments by liquid chromatography/tandem mass spectrometry

This work presents an LC–MS–MS-based method for the quantitation of nonylphenol ethoxylates (NPEOs) and octylphenol ethoxylates (OPEOs) in water, sediment, and suspended particulate matter, and three of their carboxylated derivatives in water. The alkylphenol ethoxylates (APEOs) were analyzed using isotope dilution mass spectrometry with [¹³C₆]-labeled analogues, whereas the carboxylated derivatives were determined by external standard quantitation followed by confirmation using standard additions. The method was used to study APEO’s behavior in a wastewater treatment plant (WWTP), where total dissolved NP0-16EO concentration was reduced by approximately 99% from influent (390 μg l⁻¹) to final effluent (4 μg l⁻¹), and total OP0-5EO concentration decreased by 94% from 3.1 to 0.2 μg l⁻¹. In contrast, the carboxylated derivatives were formed during the process with NP0-1EC concentrations increasing from 1.4 to 24 μg l⁻¹. Short-chain APEOs were present in higher proportions in particulate matter, presumably due to greater affinity for solids compared to the long-chain homologues. NP (0.49 μg l⁻¹) and NP0-1EC (4.8 μg l⁻¹) were the only APEO-related compounds detected in a surface water sample from a WWTP-impacted estuary; implying that 90% of the mass was in the form of carboxylated derivatives. Sediment analysis showed nonylphenol to be the single most abundant compound in sediments from the Baltimore Harbor area, where differences in homologue distribution suggested the presence of treated effluent in some of the sites and non-treated sources in the rest.     

Concentrations of chlorine, bromine and iodine in Japanese rivers

Concentrations of halogens (Cl, Br and I) in 30 Japanese rivers were measured by ion chromatography and inductively coupled plasma mass spectrometry to understand their behavior in the terrestrial environment. Concentrations of Cl, Br and I in each river, obtained at 10 sampling points from the upper stream to the river mouth, tended to increase near the river mouth. The ranges of geometric means of Cl, Br and I in each river were 1.0–19.4 mg l⁻¹, 2.5–67.9 μg l⁻¹, and 0.18–8.34 μg l⁻¹, respectively. To compare halogen behavior, the concentration ratios, Br/Cl and I/Cl, were calculated. The Br/Cl range was (2.3–7.8) × 10⁻³ (geometric mean: 3.74 × 10⁻³), and it was nearly constant except for the Yoneshiro river. It was estimated that 60–80% of total Br in the middle to lower parts of this river was the excess Br. The Br chemical form in all the rivers is generally considered to be Br⁻. The I/Cl ratios had different trends in rivers flowing into the Japan Sea and Pacific Ocean, possibly due to the different geological features in the river catchments.     

Effects of dissolved oxygen and iron aging on the reduction of trichloronitromethane, trichloracetonitrile, and trichloropropanone

Iron metal (Fe(0)) is a potent reductant capable of reducing a wide variety of halogenated organic compounds including disinfection byproducts (DBPs). These reduction reactions may play a role in DBP fate in iron water mains and potentially could be exploited to remove DBPs from drinking water or wastewater in a packed-bed configuration. Oxidants (i.e., dissolved oxygen (DO) and chlorine) present in the water, however, may decrease the DBP degradation rate by competing for reactive sites and rapidly aging or corroding the iron surface. Thus, batch experiments were performed to investigate the effect of DO on the degradation rates of selected DBPs by Fe(0). Experiments were performed under anaerobic conditions, in initially oxygen saturated buffer without DO control, and under controlled DO (approximately 4.0 or 8.0 mg l⁻¹) conditions. The effect of short-term (25–105 min) iron aging in DO-containing buffer on DBP degradation rate also was investigated in separate experiments. For fresh Fe(0), the degradation rates of trichloronitromethane (TCNM) and trichloroacetonitrile (TCAN) in initially oxygen saturated buffer were similar to their respective rates under anaerobic conditions. The degradation rate of 1,1,1-trichloropropanone (1,1,1-TCP), however, decreased significantly in the presence of DO and the effect was proportional to DO concentration in the controlled DO experiments. For a DO concentration of 4 mg l⁻¹, the degradation rate of the three DBPs was greater for longer aging times as compared to their respective rates after 25 min, suggesting the formation of a mineral phase that increased reactivity. For a DO concentration of 8 mg l⁻¹, the effects of increasing aging time were mixed. TCNM degradation rates were stable for all aging times and comparable to that under anaerobic conditions. The TCAN and 1,1,1-TCP degradation rates, however, tended to decrease with increasing aging time. These results suggest that the reduction of highly reactive DBPs by Fe(0) will not be affected by the presence of DO but that the reaction rates will be slowed by DO for DBPs with slower degradation kinetics.